Method for the heat treatment under pressure of high boiling hydrocarbons



June 19, 1934. w. RITTMEISTER 1,963,717

METHOD FOR THE HEAT TREATMENT UNDER PRESSURE OF HIGH BOILING HYDROCARBONS Filed April 27, 1932 Patented June 19, 1934 r r r I [UN T D STA-res PATENT- METHOD FOR THE HEAT TREATMENT UNDER, PRESSURE OF. HIGH BOILING HYDROQARBONS Wilhelm Rittmeister," 'Rodleben, near Rosslau,

- Germany:

Application April27, 1932, Serial No. 607,736 1 In Germany May 6, 1931 '6 Claims. (Cl. 196-53) "This-invention relates to improvements, methwhich material to be treated is introduced, this ods and apparatus for the heat treatment under pipe having a branch pipe '19 for the introduc pressure of high boiling hydrocarbons, and-'more tion of hydrogen containing gas. The lower ends particularly to the hydrogenation of these hydroof the vessels '11, 12 and 13 are each provided 5 carbons. Such materials include bituminous'mawith the pipes 20, 21 and 22 respectively, these terials, mineral oils, their distillation and extracpipes being for the purpose of withdrawing .ma-- tion products and residues or those obtained from terial for the apparatus. These pipes 20, 21 and coals, lignites and similar materials. In treat- 22 are controlled by the valves 23, 24. and 25 ment of these materials under high pressures respectively. Thedischarge passage 26 'leads 10 and temperatures considerable operating difilculty from: the. last vessel 14. The lower ends of the '65 is experienced due to the formation and separathree tubular vessels 15, 16 and 17 are provided tion of coke.- This is particularly true in crackwith 'inletpipes 27, 28 and 29 respectively, these ing processes or in the Bergius process in which pipes being adapted for the introduction of addihydrogen or hydrogen-containing gases are emtional hydrogen containing gas."

1 5 ployed at high temperatures and pressures' The i The form of construction shown inxFigure 2 Z0.

operation of such processes becomes difficult and is generally, similar to that shown in Figure '1. p bl'e if coke accumulates in the The smaller tubular reaction vessels 41, .42, 43

reaction equipment. Such coke accumulation and 44 are arranged, however, to pass upwardly causes local overheating of the equipment, plugthrough the larger cylindrical vessels 45, 46; "47

130 ging of the, pipes and tubes, frequent shutdowns and "48. This resultsin heat exchange between 75.

and becomes a source of dange While Op ati gthe vessels and also the pressure in the larger It is an object of the present invention to vessels surrounds the smaller vessels. The sizes provide an improved apparatus for the high temof the vessels are shown as difierent, the .cylin-, p'erature',high pressure hydrogenation of hydro-, drical vessels 46 andl4'7' being 'largerithan' the 5 carbonaceous .materials. P v vessels and 48 and the tubular vessels 42 and It is a further object-of this invention to pro- 43 being larger: than the vessels 41- and 44. This vide an improved apparatus of such design that results in lower velocity inthe-intermediate porthe ac'cumulation'of coke will be avoided in the tion of the flow of material. The pipes for. in-' high temperature high pressure hydrogenation troducing gasand materialrand for'withdrawing 130 of such materials. material inFigure 2 are similarto those shown It is an additional object to'provide a new in Figure 1. r

' and improved method of treating materials of By the use of the above apparatus, hydrocarthecharacter described whereby the deposition bons of all types, including those which form of solid carbon. will ,be prevented. y coke very easily, can be converted into low boil- 3 t iS- a sd O j o provide a method in mg materials suitable for use as motor fuels .or

whichnthe materials and reagents will .be rehigher'boiling materials suitable'for use as lubripeatedly .mixed during the process whereby a cants without coke formation if the opera'tionis thorouglrand continued contact between. them continuous and" takes place in the pr'esenc'e'of will be assured. j e hydrogen orhydrogen containing gases in xverti- 0 ot r a .furt rc i tsw l pp ar. as the cal tubular'reaction vessels. The reaction vesi); description proceeds. sels are connected in lsuch a way that the prod- I have shown certain preferred embodiments uctsi. being treated flow downward through a v Z of my invention somewhat diagrammatically in vessel of relatively large diameter and upward the accompanying drawing, in. which- I through atubular vessel of relatively small diam- 45 Figure 1 is a vertical. section of. one form 0 eter. Thus in this operation the reacting mate- 1 90 apparatus and e rials enteratthe top of the large vesseland are Figure 2 is a similar view of a modified form withdrawn at the bottom and rise'through the of apparatus. l s '7 tubular vessel. The velocity of the materials in Referring first to the form of, construction the tubular vessel is high in comparison with that 50 shown in Figure 1, the apparatus comprises relobtaining in the large vessel. In the operation v at v y W e Cylindrical reaction Vessels 11, 12, the materials which are liquid under the condi- 13 and 14, and the relatively narrow tubular retions of the reaction and which tend to polyaction vessels 15, 16 and 17, which are connected merize to form coke fall rapidly to the bottom of between the cylindrical vessels. The upper endv the large reaction vessel from which point they of vessel 11 is providedwith the pipe .18" through are removed by the gaseous and vaporous rejac- 1 tion products and pass upward through the tubular vessel at a relatively high velocity. In this way the materials which would tend to form coke are prevented from settling out during the treatment or from accumulating in any part of the equipment, and pass rapidly through the reaction system while the gaseous and vaporized materials have ample time to be converted into low boiling hydrocarbons. A further advantage resulting from the use of this equipment results from the intimate mixing obtained between the materials being treatedand the hydrogen containing gas at the point of withdrawal from the large reaction vessel and through the tubular vessel.

It is also advisable in some cases to use known agents for the prevention of coke formation in this operation. Such agents may include anthracene oil or hydrogenated tar or, in some low ternperature operations, naphthalene oil. These materials serve as solvents for highly asphaltic materials and prevent them from settling out. The efficiency of the process may also be improved by the use of catalysts or of contact masses which may be fixed in the vessels of wide diameter.

In the construction of this apparatus it is desirable to make the volume of the large vessels sufficient to insure the formation of high yields of low boiling materials when. operating at low temperatures. The diameter of the tubular vessels may vary in a limited range. The ratio of the diameters of the large and the tubular vessels must be such as to insure a much higher velocity in the tubular vessel than that which obtains in the larger vessel. The ratio of the diameter of the larger vessel to that of the tubular vessel may be in the order of ten to one, but this may vary depending on the throughput desired in the equipment.

The reaction units may be arranged in a series of alternating large and tubular vessels as shown in Figure 1. It is possible to vary the diameters of the various vessels in the series both in the large and in the tubular vessels, as shown in Figure 2. In this manner it is possible to vary the velocity of the materials in the various stages of the reaction and maintain a high flow rate where there is a tendency for coke forming materials to deposit.

It is also possible to maintain difierent temperatures in different reaction vessels and in some units of the series it may be desirable to maintain a temperature in the tubular reaction vessel through which the oil flows upward at such a point that substantially no reaction takes place while in the wide vessels by virtue of catalytic masses of the desired type of catalytic activity virtually all the reactions take place. By controlling the temperature in another manner it will. be possible to obtain the greater part of the cracking desired in the tubular vessels and obtain the hydrogenation in the wide vessel.

The drawing is diagrammatic and these reaction vesselsmay be arranged in any suitable way and maybe arranged in stellar form or otherwise or the narrow reaction vessel may be contained within the larger vessel as shown in Figure 2.

In the operation of the apparatus the material to be treated enters at point 18 after having been raised to a suitable temperature and pressure.-

At this point it may or may not be admixed with a hydrogen containing gas. A suitable quantity of hydrogen containing gas may be introduced through pipe 19 and the mixture of the material to be treated and the gas pass to the first hydrogenation vessel 11. This is a relatively wide vessel and theliqui'ds in thecharging material quickly fall to the bottom and are swept out of. vessel. 11 into the tubular reaction vessel 15. Additional hydrogen containing gas may be introduced through pipe 27. The materials rise rapidly through the tubular vessel 15 and enter the second vessel 12 of relatively wide diameter. Again: the liquid materials are swept out oi the vessel, pass through the tubular vessel 16 to wide vessel 13' and so on through 17 and 14 and discharge through pipe 26. Hydrogen containing gas may be introduced through pipe 28 and/or 29 depending on the type of reaction desired. When desirable it is possible to withdraw liquid materials from any or all points 20, 21 and 22.

The mixture of gas, vapors and liquid products leaving through pipe 26 are reduced in pressure after suitable cooling, the gas recovered and the liquids separated into the desired products by fractional distillation. The gas may be treated for purification and hydrogen enrichment in any suitable manner and recycled to the hydrogenation reaction. Heavy materials recovered from the distillation may be recycled to the reaction vessels in admixture with the in equipment as described containing four relatively wide reaction tubes through which the oil flowed downward and four relatively narrow tubes through which the oil flowed upward connested in series and alternating from the wide to the narrow tubes. The reaction took place under 200 atm. of hydrogen pressure and at a temperature of 460 C. After running'for 150 hours the operation was stopped and the equipment opened. No coke was found. The gas oil had a gravity of 0.85? and the following boiling range:

Per cent To 230 C 2 250 C 9 300 C 51 330 C 71.5 360 C 85.0

falling through the reaction High sulphur west Texas gas oil was treated (1.3

The oil obtained by the treatment had a gravity of 0.820 and the following boiling range:

' Per cent To 200 C 42 250 C 60 may be similarly modified. Such'changes and modifications of both method and apparatus are contemplated as will come within the spirit and connected chambers alternately larger and smaller in cross-sectional area, the flow being downward through the larger chambers and upward through the smaller chambers, the volume of the larger chambers being sufiicient to permit reaction time for the material therein, and the cross sectional areas of the smaller chambers being such that the gases and hydrocarbons pass together without substantial delay from the bottom of one large chamber through the adjacent small chamber to the top of the succeeding large chamber to avoid the deposition of coke.

2. The method of hydrogenating high boiling hydrocarbons, which comprises treating them at temperatures of approximately 460 C. and under pressures of approximately 200 atmospheres in contact with hydrogen containing gases in a series of connected chambers alternately larger and smaller in cross sectional area, the flow being downward through the larger chambers and upward through the smaller chambers, the volume of the larger chambers being sufficient to permit reaction time for the material therein, and the cross sectional areas of the smaller chambers being such that the gases and hydrocarbons pass together without substantial delay from the bottom of one large chamber through the adjacent small chamber to the top of the succeeding large chamber to avoid the deposition of coke;

together without substantial delay from the bottom of one large chamber through the adjacent small chamber to the top of the succeeding large chamber to avoid the deposition of coke.

4. The method of hydrogenating high boiling 7 hydrocarbons, which comprises treating them at temperatures of approximately 460 C. and under pressures of approximately 200 atmospheres in contact with hydrogen containing gases in a series of connected chambers alternately larger and smaller in cross sectional area, the larger chambers containing catalytic materials, the flow being downward through the larger chambersand upward through the smaller chambers, the'volume ofthe larger chambers being sufiicient to permit reaction time for the material therein, and the cross sectional areas of the smaller chambers being such that the gases and hydrocarbons p'ass' together without substantial delay from the bottom of one large chamber through the adjacent small chamber to the top of the succeeding large chamber to avoid the deposition of coke.

5. The method or" hydrogenating high boiling hydrocarbons, which comprises treating them under high temperatures and pressures in contact with hydrogen containing gases in a series of connected chambers alternately larger and smaller in cross sectional area, the flow being downward through the larger chambers and up wardthrough the smaller chambers, the volume of the larger chambers being suflicientto permit reaction time for the material therein, and the cross sectional areas of the smaller chambers being such that the gases and hydrocarbons pass together without substantial delay from the bottom of one large chamber through the adjacent small chamber to the top of the succeeding larger chamber to avoid the deposition otcoke, and adding 7 hydrogen containing gases at the bottom of the smaller chambers. 1

6, Themethod of hydrogenating high boiling hydrocarbons, which'comprises treating them at temperaturesof approximately 460 C. and under pressuresof approximately 200 atmospheres in' I contact with hydrogen containing gases in a series 1 of connected chambers alternately larger and smaller in cross'sectional area, the flow being downwardthrough the larger chambers and up' ward through the smaller chambers, the, volume of the larger chambers being suflicient to permit re- '2" action time for the material therein, and the cross sectional areas of the smaller chambers being such that the gases and hydrocarbons pass together without substantial delay from the bottom of one large chamber through the adjacent small chamber to the top of the succeeding large chamber to avoid the deposition of coke, and adding hydro gen containing gases at the bottom of the smaller chambers. v a

WILH. RI'ITMEISTER. 

